Process of making cyan-methyl derivatives of aromatic amids.



UNITED STATES PATENT OFFICE.

OTTO J. GRAUL, OF LUD\VIGSHAFEN-ON-TIIE-RllINE, GERMANY, ASSIGNOR TO BADISOI-IE ANILIN AND SODA FABRIK, OF LUD\VIGSIIAFEN-ON-'llll l- RIIINE, GERMANY, A CORPORATION OF GERMANY.

PROCESS OF MAKING CYAN-METH-YL DERIVATIVES O F AROMATIC AMIDS.

SPECIFICATION forming part of Letters Patent No. 718,340, dated January 13, 1903. Application filed January 28, 1902. erial No. 91.635. (No specimens.)

To (ZZZ whmn may concern:

Be it known that I, OTTO J. GRAUL, docto of philosophy and chemist, a subject of the.

zo dro formaldehydeanilin. These anhyd'ro"-" formaldehyde aromatic amido substances when treated with an alkali bisulfite, such as sodium bisulfite, yield products which are termed, for instance, in the case of anilin,

anhydro-formaldehyde-anilin-sodium bisulfite, (see Eibner, Annalen (Zer Ohemz'e,

Vol. 316, page 126,) and generally they are hereinafter termed anhyd ro-formaldehydearomatic amido substance alkali bisul- 3o fite. These compounds I will hereinafter for the sake of brevity designate also as bisulfite compounds. Now I have found that if certain such bisulfite compounds be acted upon by a salt of hydrocyanic acid, such as potassium cyanid orsodium cyanid,tl1e abovementioned omega-cyan-methyl derivatives are produced.

Among the aromatic amido substances which can be employed in carrying out this 40 my invention are anilin, the toluidins, the xylidins, the naphthylamins, and anthranilic acid, (ortho-carboxy-anilin,) all of whichsubstances I desire to have hereinafter included in the generic term aromatic amido subsrstance.

For the purposes of this invention it is immaterial how the bisulfite compound to be employed is prepared.

In the preferred embodiment of my process I operate as follows: I cause formic aldehyde to act upon, say, sodium bisulfite, and upon this product I cause, say, anilin to act, and upon the so-resulting product I cause, say, potassium cyanid to act. It is immaterial, however, in What order the three substances first mentioned-namely, formic aldehyde, the bisulfite, and the aromatic amido substance are brought together, and this order may be varied without afiecting the nature of my invention.

I will further illustrate the nature of this -my invention by means of the following examples,with out, howevenwishing to limit myself to the proportions or other conditions therein given. The parts are by Weight, and

the temperature degrees refer to the centigrade-scale.

EXAMPLE 1.

Production of omega-cyan-methyl-an'ilin from am'Zin, form-21c aldehyde, sodium bisulfite, and potassium cyanid.-Mix together three hundred parts of a-solution of bisulfite of soda containing, forty (40) per cent. of that substance (NaHSO and eighty (80) parts of a commercial solution of formic aldehyde containing thirty-eight (38) per cent. of that aldehyde. To this add ninety-three (93) parts of anilin, stirring well the meanwhile and keeping the temperature "at about fifty (50) degrees. In a short time the bisulfite compound of anhydro-formaldehyde-anilin will have been formed. Now add one hundred and fifty (150) parts of caustic-soda solution containing four (4) per cent. of caustic soda (NaOH) and pour it into a solution of seventy (70) parts of potassium cyanid in three hundred (300) parts of water, and heat this mixture in a water-bath to a temperature of from forty (40) to fifty (50) degrees. After having been maintained at the above temperature for about two (2) hours the mixture is transformedintoawateryandan oil-likelayer. This oil-like layer is the desired omega-cyan-methyl-anilin, which may be separated directly 5 from the warm watery layer, or the whole may be allowed to cool, so that the oil-like layer solidifies, and the solidified portion may then be separated from the watery portion by filtration. The so-obtained omega-cyanrmemo thyl-aniliu is a'practically pure product. I may also employ other aromatic amido substances in the place of the anilin of this Example l but then the working operations should be changed, as will readily be understood by chemists, so as to suit each individual case, as will be shown in the following examples.

.EXAMPLE 2.

A. Production of the b'isu'lfite compound of cmhg d ro -formaldehyde anilin.- Introduce one hundred and five (105) parts of powdered anhydro-formaldehyde-anilin into five hundred (500) parts of a solution of bisulfite of soda containing forty (40) per cent. of that substance, (NaHSO J Heat this mixture by means of a water-bath to a temperature of from eighty (80) to ninety (90) degrees, stirring the meanwhile, until a clear solution is obtained. On cooling, the liquor the bisnlfite compound separates out in the form of white glistening leaflets.

B. Production of omega-cyawmethyl-an't- Ztn from theproduct of Example 2 A.-Introduce, while stirring, two hundred and nine (209) parts of the bisulfite compound resulting from the preceding Example 2 A into a solution of seventy (70) parts of potassium cyanid in one thousand (1,000) parts of water, and heat this mixture in the water-bath to a temperature of from forty (40) to fifty (50) degrees. After having been maintained at the above temperature for about two (2) hours the mixture is transformed into a watery and an oil-like layer. This oil-like layer is the desired omega-cyan-methy1-anilin,which may be separated directly from the warm watery layer, or the whole may be allowed to cool, so that the oil-like layer solidifies,and the solidified portion may then be separated from the watery layer by filtration. The so-obtaiued omega cyan methylauilin is a practically pure product.

EXAMPLE 3.

Production of omegacyanmethyl-anil'in f0on ctnhydrogbr'maZdchyde-anilin in one 013-,

1 bath to a temperature of eighty (80) degrees until complete solution is efl'ected. Now filter off any suspended impurity and add five hundred (500) parts of water and three hundred and seventy (370) parts of a cold solution of caustic soda containing ten (10) per cent. of caustic soda, (NaOH.) Now cool the liquid to a temperature of fifty degrees and pour it into a solution of seventy parts of potassium cyanid in three hundred (300) parts of water. The omega-cyan-methyl anilin separates out almost immediately from the clear solution as an oil-like layer and may be separated from the watery layer, as described in Example 1.

In place of the anhydro-formaldehyde-anilin corresponding amounts of other anhydroformaldehyde aromatic am-ido substances may be employedsuch as the anhydro-formaldehydes of the toluidins, xylidins, &c.- and the working operations should be changed, as will readily be understood by chemists, so as to' best suit each individual case.

EXAMPLE 4.

A. Production of abtsulfite compowndjrom btsulfite of soda, aZpha-naphthylamtn, and

formic aldehyde-Produce a paste by rub- 4 bing up one hundred and forty-five (145) parts of alpha-naphthylamin with fifteen hundred (1,500) parts of an aqueous solution of sulfurous acid containing three (3) per cent. of that acid. Now gradually introduce this paste into the result of mixing formic aldehyde and bisulfite of. soda, (obtained as described in Example 1,) being careful to prevent the temperature of the mixture from rising above ten (10) degrees by some. means, such as external cooling. The bisulfite compound is formed almost immediately upon mixing.

In place of the above-described paste of naphthylamin I may also employ a concentrated alcoholic solution of naphthylamin.

B. Production of omega-cyan-methyZ-alpha-naphthylamin.--Free the bisulfite compound arising from preceding Example 4 A from sulfurous acid and bisulfite of soda as far as practicable by washing with water. Convert it into a paste by rubbing it up with five hundred (500) parts of water, and to this paste add an aqueous solution of seventy (70) parts of potassium cyanid in three hundred (300) parts of water. Digest the whole on a boiling-water bath until the oil-like layer, which forms no longer, increases in volume.

This oil-like layer is the desired omega-cyan- EXAMPLE 5.

Production of omego.-cyan-methyZ-anthran'tt tc actd.Dissolve one hundred and thirtyseven (137) parts of anthranilic acid in forty (40) parts of caustic soda dissolved in one thousand (1,000) parts of water. 0001 this solution thoroughly by means of ice and gradually add to it seventy-nine (79) parts of formic aldehyde, (containing thirty-nine per cent. of the aldehyde,) taking care that the temperature does not rise above ten (10) de- IIO grees. Now precipitate the anhydro compound by means of one hundred and fifty (150) parts of hydrochloric acid containing twenty-five per cent. of hydrochloric acid, (HCL) Convert the anhydro-formaldehyde-anthranilic acid so obtained into its bisulfite com pound,as described inExample 2 A. Filter and press the bisulfite compound thus obtained from one hundred and thirty-seven (137) parts of anthranilic acid, and then rub it up to a paste with one thousand (1,000) parts of water and render the result neutral to litmus paper by means of carbonate of soda or of bicarbonate of soda. Now gradually add to this clear neutral solution, while Ill aintaining its temperature between forty and fifty degrees, a solution ofseventy (70) parts of potassium cyanid in two hundred (200) parts of water. The reaction is soon completed. Precipitate the omega cyanmethyl-anthranilic acid from the resulting solution by means of a sufficient quantity of hydrochloric acid of suitable strength. The product so obtained is practically pure and is identical with tho product of United States Letters atent No. 662,754, of November 2' 7, 1900. A In plaice of the potassium cyanid of thepreceding examples sodium cyanid may be em ployed.

What Iclaim is- 1. The described process of making omegacyan-methyl derivative of an aromatic amido substance which consists in acting. upon a hereinbefore defined aromatic amido substance with formic aldehyde and an alkali [SEAL] Corrections in Letters Patent No. 718,340.

bisulfite and then acting upon this product with a salt of hydrocyanic acid.

2. The described process of making omega-' cyan-methyl derivative of an aromatic ainido substance which consists in acting upon a hereinbefore-defined anhydro-formaldehyde-- aromatic-amido substance with an alkali bi sulfite and then acting upon this product w ith a salt of hydrocyanic acid.

3. The described process of making omegacyan-methyl derivative of an aromatic amide substance which consists in acting upon a hereinbefore-defined anhydro-formaldehydearomatic amido substance alkali bisulfite with a salt of hydrocyanic acid.

4. The described process of making omegacyan-methyl-anilin which consists in acting upon anilin with formic aldehyde and sodium bisulfite and then acting upon this product with potassium cyanid.

5. The described process of making omegacyan-methyl-anilin which consists in acting upon anhydro-formaldehyde-anilin with sodium bisulfite and then/acting upon this product with potassium cyanid.

6. The described process of making omegaoyan-methyl-anilin which consists in acting upon anhydro-formaldehyde-anilin-sodium bisulfite with potassium cyanid.

In testimony whereof I have hereunto set my hand in the presence of two subscribing witnesses.

OTTO J. GRAUL.

I Vitnesses:

BERNI-IARD O. HESSE, JACOB ADRIAN.

F. I. ALLEN,

Commissioner of Patents.

It is hereby certified that in Letters Patent No. 718,340, granted January 13, 1903, upon the application of Otto J. 'Graul, of Ludwigshafen-on-the-Rhine, Germany, for an improvement in Process of Making Cyan-Methyl Derivatives of Aromatic Amids, errors appear in the printed specification requiring correction, as follows: In lines 32, 39, 46, 52, 57, and 62, page 3, the words The described, commencing each 7 claim, should be stricken out, and the following word process should commence with a capital P and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 6th day of October, A. D., 1903.

Corrections in Letters Patent No. 718,340.

It is hereby certified that in Letters Patent N0. 718,340, granted January 13, 1903, upon the application of Otto J. Graul, of Ludwigshafen-on-the-Rhine, Germany, for Process of Making Cyan-Methyl Derivatives of Aromatic an improvement in Amids, errors appear in the printed specification requiring correction, as follows: In

lines 32, 39, 46 5'2, 57, and 62, page 3, the words The described, commencing each claim, should be stricken out, and the following word process" should commence r with a capital P; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Otficev Signed and sealed this 6th day of October, A. D., 1903.

[SEAL] F. I. ALLEN,

Commissioner of Patents. 

